EP4144875A1 - Alliage de magnésium pour roue et son procédé de préparation - Google Patents

Alliage de magnésium pour roue et son procédé de préparation Download PDF

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Publication number
EP4144875A1
EP4144875A1 EP22182979.9A EP22182979A EP4144875A1 EP 4144875 A1 EP4144875 A1 EP 4144875A1 EP 22182979 A EP22182979 A EP 22182979A EP 4144875 A1 EP4144875 A1 EP 4144875A1
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EP
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Prior art keywords
alloy
magnesium alloy
temperature
magnesium
smelting
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Pending
Application number
EP22182979.9A
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German (de)
English (en)
Inventor
Lixin HUANG
Zuo Xu
Meng Li
Tieqiang Chen
Hanqi Wu
Qingzhu Zhang
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CITIC Dicastal Co Ltd
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CITIC Dicastal Co Ltd
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Filing date
Publication date
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Publication of EP4144875A1 publication Critical patent/EP4144875A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/02—Making non-ferrous alloys by melting
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21D—WORKING OR PROCESSING OF SHEET METAL OR METAL TUBES, RODS OR PROFILES WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21D22/00—Shaping without cutting, by stamping, spinning, or deep-drawing
    • B21D22/14—Spinning
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21D—WORKING OR PROCESSING OF SHEET METAL OR METAL TUBES, RODS OR PROFILES WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21D37/00—Tools as parts of machines covered by this subclass
    • B21D37/10—Die sets; Pillar guides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21J—FORGING; HAMMERING; PRESSING METAL; RIVETING; FORGE FURNACES
    • B21J1/00—Preparing metal stock or similar ancillary operations prior, during or post forging, e.g. heating or cooling
    • B21J1/06—Heating or cooling methods or arrangements specially adapted for performing forging or pressing operations
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21K—MAKING FORGED OR PRESSED METAL PRODUCTS, e.g. HORSE-SHOES, RIVETS, BOLTS OR WHEELS
    • B21K1/00—Making machine elements
    • B21K1/28—Making machine elements wheels; discs
    • B21K1/40—Making machine elements wheels; discs hubs
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/02—Making non-ferrous alloys by melting
    • C22C1/03—Making non-ferrous alloys by melting using master alloys
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C23/00—Alloys based on magnesium
    • C22C23/02—Alloys based on magnesium with aluminium as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/06—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of magnesium or alloys based thereon

Definitions

  • the present invention relates to the field of metal materials and metal material processing, in particular to a spun magnesium alloy with low cost and a preparation method thereof.
  • magnesium density is about 1.74 g/cm 3 , which is 2/3 of aluminum and 1/4 of steel.
  • magnesium alloy is the lightest metal structural material available so far, and has advantages of high specific strength and rigidity, shock absorption, electromagnetic shielding and radiation resistance, easy cutting processing and green recycling. It has broad application prospects in automobile, electronics, electrical appliances, transportation, aerospace and other fields. It is a lightweight metal structural material developed after steel and aluminum alloy, and can also be developed into functional materials such as biomedical materials and air batteries, and is known as a green engineering material in the 21st century.
  • Mg-AI alloys are mainly commercial alloys such as AZ31, AM60, AZ61, AZ80 and AZ91, which have become the most widely used commercial magnesium alloys.
  • magnesium has to be machined and deformed at higher temperature because its closely packed hexagonal crystal structure is not as plastic as that of face-centered cubic or body-centered cubic mechanism slip system at ⁇ 200°C.
  • Magnesium alloys have low strength and plasticity at room temperature, and it is difficult to give attention to both, which restricts the wide application of magnesium alloys.
  • increasing the processing temperature not only tends to coarsen grains and reduce the overall mechanical properties of materials, but also further increases the processing cost. Therefore, the development of magnesium alloy materials with excellent formability at room temperature or lower temperature can greatly promote the wide application of magnesium and its alloys in automobile, rail transit, aviation and other fields, and has important practical significance for expanding the application fields of magnesium alloys.
  • Application Publication number CN101381831A provides a high plasticity magnesium alloy, which contains 80 ⁇ 83% of magnesium, 12 ⁇ 15% of zinc and 2 ⁇ 8% of zirconium, 23 ⁇ 27% of lithium by mass, 7 ⁇ 9% of manganese by mass and 4 ⁇ 6% of yttrium by mass.
  • the alloy contains a large amount of lithium, so it is necessary to vacuumize or pass argon protection first in the smelting process, and meanwhile strictly control the oxygen content; on the other hand, there are a lot of rare earth elements yttrium and lithium in the alloy, which makes the alloy expensive.
  • the patent of application publication number CN102925771A provides a magnesium alloy material with high room temperature plasticity and a preparation method thereof: Li: 1.0 ⁇ 5.0%, Al: 2.5 ⁇ 3.5%, Zn: 0.7 ⁇ 1.3%, Mn: 0.2 ⁇ 0.5%, impurities ⁇ 0.3%, and magnesium as the balance. Pure lithium and AZ31 magnesium alloy were melted under vacuum and inert gas. The elongation of the alloy is 14% ⁇ 31% at room temperature. Similarly, the smelting process of the alloy is complex, and the overall room temperature elongation is still low.
  • the patent of application publication number CN102061414A provides a high plastic magnesium alloy and a preparation method thereof.
  • the composition of the magnesium alloy is: Al: 0.5 ⁇ 2%, Mn: 2%, Ca: 0.02 ⁇ 0.1%, the balance is magnesium, and the room temperature elongation of the magnesium alloy can reach 25%. Although the cost of the alloy is low, the elongation is still low.
  • These existing inventions with high room temperature plasticity still provide low room temperature plasticity.
  • magnesium alloy materials with excellent room temperature plasticity prepared by simple production and processing process which will greatly expand the advantages of abundant magnesium reserves in China and have great national economic and social significance.
  • forged magnesium alloy wheel hubs are often manufactured by traditional forging process, in which spokes and wheel rims are obtained by forging process.
  • the traditional forging process needs super-large tonnage forging equipment, result in high processing risk, large metal loss and high cost.
  • Using forging and spinning process can greatly improve the metal utilization rate and reduce the tonnage of forging equipment.
  • the wheel rim part in forging and spinning process is formed by spinning process. Because the die is not easy to heat in spinning process, even if the forging blank of magnesium alloy is heated in advance, it will still lose a lot of heat in the spinning process, so the spinning process requires high low temperature formability of magnesium alloy.
  • ZK30 magnesium alloy which has excellent spinning performance at low temperature, has high preparation cost due to the addition of Zr element. Therefore, there is an urgent need for a low-cost magnesium alloy which can be spun at low temperature and has excellent mechanical properties.
  • the present invention aims to provide a magnesium alloy for wheels and a preparation method thereof, which enables the magnesium alloy to have good low-temperature spinning performance (temperature ⁇ 360°C) and excellent strength and plasticity after molding. Meanwhile the content of light rare earth is low, the cost of the raw materials and processing is low, and it is easy to realize mass production.
  • a magnesium alloy for wheels comprising: Al: 2 ⁇ 3.0wt.%; Zn: 0.5 ⁇ 1.0wt.%; Mn: 0.3 ⁇ 0.5wt.%; Ce: 0.15 ⁇ 0.3wt.%; La: 0.05 ⁇ 0.1wt.%, the balance is Mg.
  • unavoidable impurities are also included.
  • a method of preparing a magnesium alloy comprises the following steps: (1) batching, in terms of the mass percentage: Al: 2 ⁇ 3.0wt.%; Zn: 0.5 ⁇ 1.0wt.%; Mn: 0.3 ⁇ 0.5wt.%; Ce: 0.15 ⁇ 0.3wt.%; La: 0.05 ⁇ 0.1wt.%, the balance is Mg for batching; (2) smelting, putting the pure Mg ingot into a crucible of a smelting furnace, setting the furnace temperature at 700 ⁇ 730°C and keeping it, adding the pure Al block and pure Zn block preheated to 50 ⁇ 80°C into magnesium solution after melting, then raising the smelting temperature to 760°C, adding Al-Mn master alloy, Mg-Ce-La master alloy and Mg-Ce master alloy preheated to 50 ⁇ 80 °C into magnesium solution respectively; then raising the smelting temperature to 780°C, keeping the temperature for 5 ⁇ 15 minutes, stirring for 3
  • the smelting process is carried out under the protection of a mixed gas of CO 2 and SF 6 .
  • the surface scum needs to be removed and pour into a die to obtain a magnesium alloy.
  • the processes of cutting into blanks and peeling are also included before extrusion.
  • the stirring in the smelting process includes mechanical stirring and/or argon stirring.
  • the Al-Mn master alloy is an Al-20Mn master alloy
  • the Mg-Ce-La master alloy is a Mg-15Ce-10La master alloy
  • the Mg-Ce master alloy is a Mg-30Ce master alloy.
  • a mixed gas of CO 2 and SF 6 has a composition volume ratio of 50 ⁇ 100: 1.
  • a process for preparing a wheel according to the magnesium alloy includes the following steps:
  • the prepared alloy has good high-temperature oxidation resistance, and can be poured and heat treated without protective gas under the condition of the present invention.
  • the alloy is a new type of Mg-Al-Mn-La-Ce alloy with low aluminum, high manganese and light rare earth.
  • the technical solution of the present invention is: a magnesium alloy for wheels, the alloy is Mg-Al-Zn-Mn-La-Ce alloy, and the chemical composition mass percentage is: Al: 2 ⁇ 3.0wt.%; Zn: 0.5 ⁇ 1.0wt.%; Mn: 0.3 ⁇ 0.5wt.%; Ce: 0.15 ⁇ 0.3wt.%; La: 0.05 ⁇ 0.1wt.%, the balance is Mg and unavoidable impurities.
  • a method for preparing the magnesium alloy comprises the following steps.
  • the Al-Mn master alloy is an Al-20Mn master alloy.
  • the Mg-Ce-La master alloy is a Mg-15Ce-10La master alloy.
  • the Mg-Ce master alloy is a Mg-30Ce master alloy.
  • composition volume ratio of the mixed gas of CO 2 and SF 6 is 50 ⁇ 100: 1.
  • a process for preparing a wheel according to the magnesium alloy comprises the following steps: (1) forging and spinning: forging the shaped magnesium alloy material described in the previous step on a 6000-ton forging equipment at a forging temperature of 320 ⁇ 420°C; (2) spinning the wheel rim at a spinning temperature of 260 ⁇ 360°C after forging, and finally the magnesium alloy wheel hub is obtained.
  • the die is a die for forming bars, plates, tubes, wires or profiles.
  • the present invention is characterized in that: grain refinement can be generally adopted in the magnesium alloy, and quantity and size of precipitated strengthening phase in the alloy can by adjusted to improve the room temperature strength and plasticity of the alloy, such as optimizing the alloy texture, etc.
  • the technical principle of the present invention is that: low Al and high Mn in alloying elements, Al-Mn precipitated phase is obtained during homogenization of alloy, Al-Mn precipitated phase can pin the grain boundary and inhibit the migration of grain boundary.
  • Rare earth elements will segregate at the interface of Al-Mn precipitated phase, which can improve the morphology and distribution of AIMn phase during solidification, inhibit its coarsening during extruding and forging, and help to refine grain and enhance strength. Adding light rare earth can also achieve the purpose of refining Al-Mn particles.
  • Al 2 ⁇ 3.0wt.%: when the content of Al is less than 2wt.%, the Al is completely solid-dissolved in the magnesium matrix, cannot form a precipitated phase with Mn, and does not have a strengthening effect; when the content of Al is more than 3wt.%, the Al element will be enriched at the grain boundary, which will hinder grain deformation. Many practices have proved that materials with high Al content are prone to fracture during spinning.
  • Zn 0.5 ⁇ 1.0wt.%; an appropriate amount of Zn will combine with Al, Ce and La to form a precipitated phase with higher strengthening effect.
  • Mn 0.3 ⁇ 0.5wt.%; when the content of Mn is less than 0.3wt.%, the amount of formed Mn-rich phase is small, which is not enough to hinder the growth of grains and improving the strength is limited; when the content of Mn is more than 0.5wt.%, the formed Mn-rich phase is easy to segregate and cause cracking.
  • Ce 0.15 ⁇ 0.3wt.%
  • La 0.05 ⁇ 0.1wt.%
  • the addition of these two light rare earth elements is due to the fact that Ce and La atoms dissolved in magnesium alloy matrix tend to segregate at the interface of nano-scale Mn-rich precipitated phase due to the large difference between atomic size and Mg atom size, thus reducing the free energy.
  • the occurrence of segregation can effectively inhibit the coarsening of nano-scale Mn-rich phase during extruding and forging. It is beneficial to enhance the grain refinement of nano-scale Mn-rich phase.
  • the deformed magnesium alloy material is finally obtained and the magnesium alloy wheel hub is prepared by forging and spinning process.
  • the tensile yield strength of wheel rim at room temperature reaches 190 MPa
  • the tensile strength reaches 280 MPa
  • the elongation rate is over 15.8%.
  • the magnesium alloy wheel hub manufactured by the conventional Al-Zn-Mn alloy (AZ31 alloy: Al: 2.5 ⁇ 3.5wt.%; Zn: 0.6 ⁇ 1.4%; Mn: 0.12 ⁇ 1.0%) by means of the same forging and spinning process has poor quality stability, and transverse micro-cracks occur in wheel rims of some wheel hubs.
  • the tensile yield strength at room temperature reaches 133 MPa, yield strength is 242 MPa and elongation is 8.7%.
  • Embodiment 1 The Mg-2AI-0.7Zn-0.5Mn-0.3Ce-0.1La (wt.%) alloy composition ratio is selected to form magnesium alloy, and the preparation method comprises the following steps.
  • a sample with a length of 70 mm is cut from the wheel rim part of the wheel hub obtained in embodiment 1, and is processed into a round bar-shaped tensile sample with a diameter of 5 mm and a gauge length of 32 mm for tensile test.
  • the axial direction of the round bar of the sample is the same as the extrusion streamline direction of the material.
  • Measurement result of the magnesium alloy is that the tensile strength is 280 MPa, the yield strength is 190 MPa, and the elongation is 15.8%, as shown in Table 1.
  • the magnesium alloy obtained in the embodiment has both high strength and high elongation.
  • a typical tensile curve of the magnesium alloy obtained in the embodiment is shown in Fig. 1. Fig.
  • Embodiment 2 shows the microstructure morphology of Mg-2AI-0.7Zn-0.5Mn-0.3Ce-0.1La (wt.%) magnesium alloy prepared in the embodiment parallel to the extrusion direction. It can also be seen from the metallographic diagram that the alloy undergoes complete dynamic recrystallization during spinning, and the grain size is about 8 ⁇ m.
  • Embodiment 2 The Mg-2.6AI-0.9Zn-0.36Mn-0.2Ce-0.05La (wt.%) alloy composition ratio is selected to form magnesium alloy, and the preparation method comprises the following steps.
  • the preparation of the wheel from the magnesium alloy material comprises forging and spinning: (1) forging the shaped magnesium alloy material described in the previous step on 6000-tons forging equipment at a forging temperature of 370°C; (2) spinning the wheel rim at a spinning temperature of 350°C after forging, and finally the magnesium alloy wheel hub is obtained.
  • a sample with a length of 70 mm is cut from the wheel rim part of the wheel hub obtained in embodiment 2, and is processed into a round bar-shaped tensile sample with a diameter of 5 mm and a gauge length of 32 mm for tensile test.
  • the axial direction of the round bar of the sample is the same as the metal streamline direction of the material.
  • Measurement result of the magnesium alloy in the present invention is that the tensile strength is 270.3 MPa, the yield strength is 172.1 MPa, and the elongation is 11.9%, as shown in Table 1.
  • the magnesium alloy obtained in the embodiment has both high strength and high elongation.
  • a typical tensile curve of the magnesium alloy obtained in the embodiment is shown in Fig. 1. Fig.
  • Embodiment 3 The Mg-2.9Al-0.6Zn-0.4Mn-0.2Ce-0.05La (wt.%) alloy composition ratio is selected to form magnesium alloy, and the preparation method comprises the following steps.
  • the preparation of the wheel from the magnesium alloy material comprises forging and spinning: (1) forging the shaped magnesium alloy material described in the previous step on 6000-tons forging equipment at a forging temperature of 390°C; (2) spinning the wheel rim at a spinning temperature of 360°C after forging, and finally the magnesium alloy wheel hub is obtained.
  • a sample with a length of 70 mm is taken from the wheel rim of the wheel hub obtained in embodiment 3, and the sample is processed into a round bar-shaped tensile sample with a diameter of 5 mm and a gauge length of 32 mm, and the axial direction of the sample round bar is the same as the metal streamline direction of the material.
  • Measurement result of the magnesium alloy in the present invention is that the tensile strength is 273 MPa, the yield strength is 178 MPa, and the elongation is 11.4%.
  • the magnesium alloy obtained in the embodiment has both high strength and medium elongation.
  • a typical tensile curve of the magnesium alloy obtained in the embodiment is shown in Fig. 1 .
  • Fig. 4 shows a microstructure morphology of Mg-2.9AI-0.6Zn-0.4Mn-0.2Ce-0.05La (wt.%) magnesium alloy prepared in this embodiment parallel to the extrusion direction. It can also be seen from the metallographic diagram that its characteristics are similar to those of embodiments 1 and 2, and the alloy undergoes complete recrystallization during extruding, with a grain size of about 15 ⁇ m.
  • Fig. 5 is a TEM microstructure diagram of an alloy in the embodiments. From the diagram, it can be found that MgRE phase exists near the nano-scale Mn-rich phase, which will hinder the coarsening of the nano-scale Mn-rich phase in the subsequent heat treatment. Meanwhile, it can be observed that there are more nano-scale precipitates in the alloy, which occur prematurely, thus improving the room temperature plasticity of the alloy.
  • the comparative example is a commercial AZ31 magnesium alloy: Mg-2.8AI-0.9Zn-0.3Mn (wt.%) magnesium alloy.
  • a typical stress-strain curve in a tensile test is shown in Fig. 1 . Its tensile strength is 242 MPa, its yield strength is 133 MPa, and its elongation is 8.7%, as shown in Table 1.
  • the room temperature strength and elongation of the new magnesium alloy in the present invention are significantly improved compared with the comparative alloy.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
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  • Metallurgy (AREA)
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EP22182979.9A 2021-09-03 2022-07-05 Alliage de magnésium pour roue et son procédé de préparation Pending EP4144875A1 (fr)

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EP (1) EP4144875A1 (fr)
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CN117620049B (zh) * 2024-01-25 2024-05-31 山西神舟航天科技有限公司 一种高稀土含量镁合金v型结构件的制备方法

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CN1425785A (zh) * 2003-01-08 2003-06-25 华南理工大学 一种含稀土的镁铝锌合金及其制备方法
CN101381831A (zh) 2008-10-29 2009-03-11 仝仲盛 一种高塑性镁合金
CN102061414A (zh) 2010-12-31 2011-05-18 重庆大学 高塑性镁合金及其制备方法
CN102925771A (zh) 2012-10-31 2013-02-13 重庆大学 高室温塑性镁合金材料及其制备方法
CN104109787A (zh) * 2013-04-18 2014-10-22 嘉兴中科亚美合金技术有限责任公司 适用于板材的含铈变形镁合金及制备方法
CN109182861A (zh) * 2018-11-08 2019-01-11 中信戴卡股份有限公司 一种塑性变形镁合金及其制备方法

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CN1329539C (zh) * 2005-06-24 2007-08-01 宁波博威集团有限公司 无铅易切削低锑铋黄铜合金及其制造方法
CN102787264A (zh) * 2012-05-24 2012-11-21 刘利涛 一种高强度高塑性镁合金材料及其制备方法
CN106834766B (zh) * 2015-12-03 2018-11-30 北京有色金属研究总院 一种制备大尺寸高合金元素含量镁合金铸锭的方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1425785A (zh) * 2003-01-08 2003-06-25 华南理工大学 一种含稀土的镁铝锌合金及其制备方法
CN101381831A (zh) 2008-10-29 2009-03-11 仝仲盛 一种高塑性镁合金
CN102061414A (zh) 2010-12-31 2011-05-18 重庆大学 高塑性镁合金及其制备方法
CN102925771A (zh) 2012-10-31 2013-02-13 重庆大学 高室温塑性镁合金材料及其制备方法
CN104109787A (zh) * 2013-04-18 2014-10-22 嘉兴中科亚美合金技术有限责任公司 适用于板材的含铈变形镁合金及制备方法
CN109182861A (zh) * 2018-11-08 2019-01-11 中信戴卡股份有限公司 一种塑性变形镁合金及其制备方法

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CN113802038B (zh) 2022-11-25
CN113802038A (zh) 2021-12-17
US11905577B2 (en) 2024-02-20
KR20230034855A (ko) 2023-03-10

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